Hydrazine and aluminum containing explosive compositions



United States Patent 3,523,047 HYDRAZINE AND ALUMINUM CONTAINING EXPLOSIV E COMPOSITIONS Robert M. Bridgforth, Jr., and ,George S. Sutherland, Mercer Island, Michel E. Maes, Bellevue, and David L. Laster and Gerald L. Hurst, Issaquah, Wash., assignors to Explosives Corporation of America, Issaquah, Wash, a corporation of Washington No Drawing. Continuation-impart of application Ser. No. 340,127, Jan. 27, 1964.This application Dec. 30, 1968, Ser. No. 787,997

Int. Cl. C06b 1/04, 15/00 US. Cl. 149-36 61 Claims ABSTRACT OF THE DISCLOSURE Explosive compositions characterized by very high detonation velocities, excellenteratering performance, high blast effect, and useful impact sensitivity characteristics, and comprising hydrazinium nitrate or mixtures of hydrazinium nitrate and ammonium nitrate (with optional minor proportions of alkali metal nitrates and/or alkali metal perchlorates and/or calcium nitrate and/or calcium perchlorate), togetherwith hydrazine or mixtures of hydrazine and ammonia, and with finely divided aluminum as a reducer reactant. The explosive composition' can further comprise optional physical property modifying additives, such as desensitizing agents, thickening'and gelling agents, freezing point depressants, and waterproofing agents; Also presented are methods of preparation of the compositions, including the preparation of pre-mixed non-explosive components, a first such component being hydrazine or like liquid containing a nonexplosive amount of the oxidizer salt(s), and a second such component being essentially the additional oxidizer salt(s). Relative percentages by weight of the significant ingredients are as follows: Aluminum particles, from about 2% to about 45%; NH -and'-NH from 0% to about 18%; N H 'and N H +,-from about 6% to about 75%; NO;, or equivalent anion, from about 14% to about'70%. Optionally, minor proportions of the nitrate or equivalent anion can be present in the form of certain CROSS REFERENCES TO RELATED APPLICATIONS This application is a continuation-impart of Bridgforth and Sutherland US. application Ser. No. 340,127, entitled Stable, High Energy Compositions, and filed Jan. 27,

This application is also a continuation-in-part of Macs US. application Ser. No. 631,123, entitled Hydrazine Containing ExplosiveComposition's, filed Apr. 17, 1967, and issued as US. 'Pat'. No'. 3,419,443 on Dec. 31, 1968.

BACKGROUND OF. THE 'INVENTION 7 Field of the invention The invention pertains to explosive compositions and methods, characterized by a hydrazinium nitrate/hydrazine/aluminum explosive system, together with labile equilibrium amounts of ammonium nitrate and ammonia in some instances, and together with various physi-. cal property modifiers-to provide appropriate stability, density, viscosity, and freezing point characteristics in the composition.

- Description of theprior art Explosive and propellant compositions are generally known which involve mixtures of hydrazine and hydrazinium nitrate (also known as hydrazine nitrate or hydrazine mononitrate) such as are disclosed in Audrieth US. Pat.

3,523,047 Patented Aug. 4, 1970 No. 2,704,706 and Audrieth et al. US. Pat. No. 2,943,927. US. Pat. No. 2,704,706 discloses ammonium nitrate sensitized with hydrazinium nitrate for use in conjunction with a known explosive such as TNT, the nitrates being in solid form and without any free hydrazine present. In UJ'S. Pat. 2,943,927 a hydrazine-hydrazinium nitrate system is noted as having a characteristically low freezing point and having utility for use as a fuel in conjunction with conventional oxidizers such as hydrogen peroxide, fuming nitric acid and liquid oxygen, the hydrazine-hydrazinium nitrate in this instance including at least about 18% hydrazine by weight, and optimally about 50% or more by 'weight of hydrazine, to provide a freezing point for the fuel of some 50 C. In the Audrieth et al. fuel, as is above noted, the proportionation of the hydrazinehydrazinium nitrate mix is determined solely by consideration of freezing point depression, andnot by any consideration of stoichiometrie balance or maximal efiiciency as an explosive composition, and more particularly does not involve any consideration of stoichiometric balance or maximal efficiency in the situation where the hydrazinehydrazinium nitrate mix is employed in conjunction with an uncombined metal reducer constituent such as aluminum, as in the case of the present invention.

Also reviously known are explosive compositions containing ammonium nitrate, together with a hydrogen-containing solvent therefor, such as liquid ammonia or ammoniacal ammonium nitrate solutions, and with a metallic fuel constituent such as aluminum or magnesium particles, which type of explosive composition is disclosed in Hradel US. Pat. No. 3,124,495. In these compositions the ammonia or like solvent for the ammonium nitrate is present in a proportion of from about 2% to about 35% by Weight, as compared with the ammonium nitrate present in the proportion of about 10% to about 83% by weight, and the metal constituent is present in the amount of from about 15% to about 60% by Weight. In the Hradel explosive composition the particle size of the metal constituent is stated to be essentially greater than 20 US. standard sieve, in order that the composition be satisfactorily insensitive from the point of view of avoidance of premature detonation during handling. While Hradel presents a general statement as to the hydrogen-containing solvent for the ammonium nitrate being either liquid ammonia, water, ammonium hydroxide, or hydrazine (with all examples presented involving ammonia in aqueous solution as the solvent), Hradel makes no distinction with regard to various solvents, nor any comprehension as to any particularly advantageous physical properties or detonation characteristics of particular combinations of hydrazine or hydrazine containing solvent with a nitrate or the like oxidizer dissolved therein and in the presence of aluminum particles, such as characterizes the present invention. The Hradel contribution to the art is in eifect only an ammonia-ammonium nitrate/ aluminum or magnesium type explosive systempThis is apparent from the factthat hydrazine and magnesium can be exothermically unstable and yield a spontaneously combustible composition.

SUMMARY OF THE INVENTION In comparison with the Hradel explosive system, the hydrazinium nitrate/hydrazine/aluminum explosive system of the invention has free hydrazine present which, even if present in excess, is peculiarly non-deleterious to the explosive reaction, since it of itself decomposes to gaseous products with energy release, whereas the ammonia or ammonia and water liquid constituent of Hradel requires energy for decomposition and thus detracts from the explosive energy release. To be considered as well is the circumstance that hydrazine is much more than a simple solvent in the explosive system of the present invention, since it also forms unique intermediate reaction products (theorized to include AlN, for example) which result in a higher and more rapid energy release. Hydrazine also serves as a uniquely effective working fluid in the present explosive system, resulting in more energy contribution to the mixture as it reacts to gaseous end products, adding substantially more gas per initial unit weight of the composition. Perhaps of most significant importance in comparing the ammonia/ammonium nitrate/aluminum or magnesium explosive system of Hradel with the hydrazine/hydrazinium nitrate/aluminum explosive system of the present invention is the consideration that the Hradel liquor (the normally liquid portion of the composition, i.e. ammonium nitrate dissolved in ammoniacal aqueous solution) is not detonable in the absence of the metal constituent, whereas the liquor of the present invention (e.g. ammonium nitrate dissolved in hydrazine to form an ionic equilibrium of hydrazinium and ammonium cations and nitrate anions along with substantial amounts of free hydrazine and also free ammonia being present) is of itself explosive without the metal (aluminum) constituent. The explosive system of the present invention is consequently theorized to provide what may be termed a two-stage explosive system, with the initial explosive shock wave being caused primarily by the reaction of the oxidizer and the hydrazine, with the reaction of the metal constituent apparently occurring in two stages to provide an after shock. As a result of such two stage reaction of the aluminum constituent, optimized formulations characteristic of the present invention demonstrably provide about twice the air shock of TNT, whereas the air shock performance of the Hradel explosive system is about the same as that of TNT.

To further compare the nature of the respective explosive reactions of the Hradel type explosive system and that of the present invention, it is theorized that a typical Hradel type explosive reaction proceeds as follows:

Also for comparison purposes, a typical ammonium nitrate/aluminum/water explosive system is theorized as reacting as follows:

By comparison, the reactions characterized the explosive system of the present invention are theorized to be as follows:

Broad Preferred Optimized Constituent range range formula N03 or equivalent *55 38 With regard to the above constituent formulations, the nitrate ion or equivalent can be present in one or more compounds selected from the group consisting of nitrate(s) and mixtures thereof with minor amounts of perchlorate(s). Optionally, the oxidizer salt can also include minor amounts of one or more oxidizer salts having certain metallic cations in lieu of a stable hydronitrogen type caton, i.e. the oxidizer salt(s) can include a minor proportion of an oxidizer salt selected from the group consisting of alkali metal nitrates, calcium nitrate, aluminum nitrate, hydrazinium perchlorate, alkali metal perchlorates, calcium perchlorate, and mixtures thereof. However, in the usual application of the explosive composition, the presence of a minor amount of metallic cation offers no advantage and to an extent detracts from the explosive efficiency of the composition in that the metallic cation forms a solid reaction product rather than gaseous reaction product. In some instances, however, a minor amount of a metallic cation in the oxidizer salts is beneficial from the point of view of reducing foaming during composition preparation, or from the point of view of improved storage characteristics or other desired physical properties.

The explosive compositions of the present invention in general can be formulated either by mixing ammonium nitrate and hydrazine with subsequent aluminum particle addition, or by mixing hydrazinium nitrate with hydrazine with subsequent aluminum particle addition. In the first instance, the nitrate is present in the final mix in the form of hydrazinium nitrate and ammonium nitrate in labile equilibrium with hydrazine and ammonia. In the second instance the nitrate ion is present essentially in the form of hydrazinium nitrate without substantial ammonium nitrate being present. As a variation of the first manner of composition formulation, and to arrive at a composition wherein the nitrate is present essentially entirely as hydrazine nitrate with essentially no ammonium present, the mixing of ammonium nitrate and hydrazine can proceed at elevated temperature and/ or under vacuum to remove evolved gaseous ammonia. Considering the type of explosive composition resulting from the first above-discussed mode of preparation, i.e. the type of explosive composition which incorporates a mixture of hydrazinium nitrate and ammonium nitrate in labile equilibrium with hydrazine and ammonia, from the point of view of the approximate relative percentages by weight of the starting materials, the explosive compositions according to the invention include the following constituents in the following approximate percentages:

Broad Preferred Optimized Constituent range range formula Aiurfinum 2 15 20-35 33 NH4NO3- 32-70 48 NQHt 1:30 19 Broad Preferred Optimized Constituent range range formula NzfiaNOa 21-95 38-83 57 NaHi 3-77 7-30 10 Also to be considered with respect to relative proportioning is the commonly used thickening and/or gelling agent incorporated in the explosive mix. With respect to such agent, and as a percentage of the total explosive mixture by weight, the broad range of the thickening and/ or gelling agent is about O20%, the preferred range is about 1-5 and the optimized proportion is about 3%.

Thickening and/ or gelling agents are usually added to the explosive compositions of the invention to maintain the finely divided aluminum in substantially uniform distribution in the explosive mix, which is otherwise in many instances a liquid slurry by reason of the hydrazine containing solvent and dissolved oxidizer constituents being in liquid or liquid slurry form. Thickening or gelling of the composition can be accomplished by a variety of additional agents, generally known per se for the purpose, added in desired amounts up to about 20% by weight. Typical thickening and gelling agents are Cab-O-Sil (a finely divided SiO- thickening agent, suitably usable in proportions up to about 10% by weight) and Guartec 503 (a cross linking gelling agent, suitably used in proportions up to about by weight). Another useful gelling agent is Carbopol, for example. Gelling agents are commonly furnished in the form of a powder, and such hydrazine at room temperature. When this solution had normalized, the remainder of the ammonium nitrate and the thickening agent .'were added with stirring to cause substantially complete dissolution of the nitrate in the hydrazine. The aluminum powder (Reynolds atomized powder can be added to the liquid mix or a liquid con- 5 aluminum A 15ll, vvith particle sizes predominantly in stituent prior to addition of one or more of the other the range of 3 040 microns) was then progressively explosive constituents. Thus, for example, the gelling agent added while the mixture was stirred with a Lightening suitably can be added to the hydrazine along With and mixer (1750 r.p.m.) and agitation was continued until as a pre-mixed addition to the solid ammonium nitrate. 10 the viscosity of the mixture was sufficient to prevent the The addition of Guartec 503 to the explosive is also adaluminum particles from settling out. Three one pound vantageous in terms of waterproofing the explosive for charges were then prepared in each instance, the conmany usages thereof, such as ground placed applications tainer used for the Examples 1-5 being a conventional where in-place pickup of environmental water could other- B t R d one pint polyethylene b ttl A11 hot wise unduly desensitize the explosive. Carbon black i 15 were boosted with 50 gram tetryl pellets and initiated with also efiective thickening agent, and typifies agents of this D t SSS seismograph blasting caps EB, with the type which functi n With ut 21150 being a g g g detonator-booster assemblies packaged in a polyethylene In y apphgafiohs 0f the explosive Composition it bag to prevent reaction with the explosive, the polyis also desirable t add a deSenSitiZlhg agent to inhibit ethylene bottle being cut from the side above its explosive Sensitivity of the composition, either during the mehllcontents for insertion of detonator-booster assembly bag fachll'ing ProfileSS during 1159- Water is an effective and egress of the detonator leads. All charges were then sensitizer and, while it does have a pronounced effect on b i d to a depth f 20 i h i i il sandy l the energy Characteristics, Water can be a desirable earth. All charges were placed container bottom down n iti in amounts P to about y Weight in and tamped' in the blast holes, the depth of placement certain mixes. Oth r efiective desensitizihg agents are measurement being to the bottom of the explosive charge. glycerin, y a ahdval'ious hydrocarbon Oils, Such Cratering performance was measured in terms of blast 3S Stove example In theinstance of Stove Oil, the crater depth in inches to solid ground at the center of the Proportion of desensitize! can be P to about 20% of crater, and in terms of average diameter of the crater, the t tal eXP103iVe y Weight-I11 the case of a Solid the average diameter being determined by the average of but liquidifiable desensitize! Such as Wax, the desensitizer four diameters across the crater. Cratering performance of is suitably heated and mixed in the composition at elevated the various Examples 1 5 and h comparison Example X temperature, resolidifyihg and contributing to the thicken were as shown in the above tabulation. The improvement i g of the Composition 1113011 Cooling thereof- In general in cratering performance of all of the examples, in comany non-volatile material which exhibits storage stability parison with the cast TNT charge (Example X) is in adm With the hydrazine/hydrazine Salt Compof parent. Also apparent is the circumstance that the propor- DeHtS Ofthe explosive can act as a desensitizertion of aluminum is not particularly critical (comparing some explosive compositions centemplated by the P about 20% aluminum in Example 3 with about 32.7% ent invention have a freezing point near normal tempera: l i in Example 1), and that presence of a b ture and thus make it desirable to have included therein a ma amount f Water (about 5% in Example 5 does not freezing Point depressing agent Ahvexample of a compatl' 40 materially change the cratering performance (comparing ble freezing point depressant for the purpose is hy- Examples 1 and 5) drazinium thiocyanate' (N H S CN). E l 6 'The abpve and .other physlcal Property .modlfiers are To further characterize the properties of typical exi dlscilssed r.el.atlon to ydrazlmuln. hyplosive compositions, the explosive of Example 1, prepared drazlmllm filtrate cqntafmng exploslve composltlons m the 40 as above indicated, was determined to have a density of aforesald apphcatlon 1.61 at 69 F. and a sensitivity of 70 kg./cm. For com- T the i here Pertinent dlsclqsurqs 9 Sald apparison purposes, an Example 6 composition was formuphcatlon and Sa1q?atent.havmg to 1th snmlzir hydralated, involving the same ingredient proportions as in u hydrazm.lum y m t exploslv? Example 1 (except for 3 parts Cab-O-Sil), the hydrazine posmons havmg to do W1 th Vanous properiles and in this instance being preheated to 150 F. then added to characienstlcsihereof Well as the antlileqmvalency the ammonium nitrate slowly with agitation, followed by of various. actlve colisuments andv'vanous p yslcal. Pro}?- heating of the mix to 120 F. to completely dissolve all F modlfiers therem a hereby Incorporated m thls of the nitrate in the solution and to evolve gaseous amdlsclosure by f monia. This procedure resulted in a detonable composi- DESCRIPTION OF PREFERRED EMBODIMENTS tion having a comparable sensitivity and a density of A comparison example of cast TNT and various ex- 1'752 at 68 E 1 7 plosive compositions typical of the present invention I Xampe v were formulatedwith ingredient proportions as set forth To show the effect of a desensitizer on cratering erinthe following Tablel: I formance, the explosive composition of Example '1 (with v a TABLE 1 Cratering Performance (1 lb. shots buried 20' in Formulation (parts by weight) sandy loam) NzHr NH NO3. Al Other Depth Diam.

(1) 1- 33 53 40 100 68 4Cab-O-S11. 40 so 40 100 do 36 40 100 36 do 37 73 70 54 ..do 36 71 40 68 4Cab-O-Sil, 10 water" 40 84 1 Cast TNT.

In each of the instances of Examples l-5, a first nonexplosive liquid component was first prepared by dissolving about 5 parts of the ammonium nitrate in the 75 ample 1 plus 21% glycerin by weight. Performance tests 3 parts Cab-O-Sil) was compared with an Example 7 explosive composition containing the ingredients of Exshowed this mixture Was markedly desensitized but still detonatable. Specifically, the Example 1 composition yielded cratering 36 inches deep and 115 inches in diameter, while the desensitized composition yielded craten'ng 26 inches deep and 68 inches in diameter. Related tests involving variation of glycerin proportion from 16% to 22% indicated none of the compositions were cap sensitive but Were rifle impact sensitive in rubber lined cast iron pipe, with lO'W order detonations at 20% glycerin and below.

Examples 8 and '9 To further examine cratering performance of a desensitized explosive composition, an Example 8 composition Was prepared incorporating with the formulation of Example 1 5% by Weight of stove oil and an Example 9 composition was also prepared which included stove oil with the formulation of Example 1. Example 8 proved to be both rifie bullet (.30-06) impact sensitive and cap sensitive, whereas Example 9 proved both rifle impact insensitive and cap insensitive. Boosted with 50 grams tetryl, both Examples 8 and 9 proved detonable, and Example 9 produced a crater 42 /2 inches deep and 94 inches in diameter, as compared with an Example 1 formulation crater 43 /2 inches depth and 114 inches diameter.

Example 10 The formulation of Example 1 compounded with 0.1% by weight Guartec 503 and 4 parts Cab-O-Sil gave a composition with a creamy consistency low enough in viscosity to pour like a thick syrup and high enough to prevent the aluminum settling out. The combination of Guartec 503 and Cab-O-Sil proved particularly effective as a thicknening agent for the composition of Example 1.

Examples 11 and 12 To further investigate cratering performance of explosives characteristic of the present invention as comparted with known aluminum containing explosives, a series of test shots was conducted involving like amounts of the explosives of Example 1 (with 5 parts Cab-O-Sil) and Example 2, tested in like ground along with like amounts of Navy 'I-I6 explosive and tritonal explosive. H-6, as known, is a 60/40 mixture of RDX and TNT, formulated with 5% Wax and aluminum particles, by weight. As also known, tritonal is an 80/20 mixture of TNT and aluminum particles. All shots were housed in steel jugs, and the charge in each instance weighed 1 pound and was buried a depth of 20 inches. Cratering performance for these shots was as follows:

From the foregoing, and from the properties, characteristics and performance data available with respect to similar hydrazine and hydrazinium nitrate explosive compositions as presented in the aforesaid application 340,127 and US. Pat. 3,419,443, further variations in formulations, modes of formulation, and adaptations of explosive compositions of the present invention for various applications will be apparent to those skilled in the art, within the scope of the following claims.

What is claimed is:

1. An explosive composition comprising:

(a) an oxidizer reactant selected from the group consisting of (1) hydrazinium nitrate,

(2) mixtures of hydrazinium nitrate and ammonium nitrate, and with a minor amount of an oxidizer salt selected from the group consisting of alkali metal nitrates, calcium nitrate, aluminum nitrate, hydrazinium perchlorate, alkali metal perchlorates, calcium perchlorate, and mixtures thereof;

(b) as a solvent for the oxidizer and as a gas producing reactant, a hydrazine containing liquid selected from the group consisting of hydrazine and mixtures thereof with ammonia; and

(c) as a reducer reactant, finely divided aluminum;

said oxidizer and said hydrazine containing liquid being present in detonatable proportions.

2. An explosive composition comprising the following constituents, present in the following relative percentages by Weight:

Aluminum particles From about 2% to about 45%.

NH and NH 0% to about 18%.

N H and N H From about 6% to about 75%.

NO or equivalent From about 15% to about wherein the nitrate anion or equivalent is present in one or more compounds selected from the group consisting of nitrate(s) and mixtures thereof with minor amounts of perchlorate (s 3. An explosive compostion according to claim 2, wherein the aluminum particles are present in substantially stoichiometric proportion with respect to the nitrate or equivalent.

4. The explosive composition of claim 2, at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium.

5. The explosive composition of claim 2, further comprising a thickening and/or gelling agent present in an amount sufficient to provide the composition with the rheological properties of a solid and insufficient to render a composition nondetonatable.

6. An explosive composition according to claim 5, wherein said gelling agent is present in an amount less than about 10%, and is selected from the group consisting of expanded silica, Guartec, and mixtures thereof.

7. An explosive composition according to claim 2, further comprising a desensitizing agent, present in an amount insuflicient to render the composition nondetonatable.

8. An explosive composition according to claim 7, wherein said desensitizing agent is present in an amount less than about 20% by weight and is selected from the group consisting of water, glycerin, glycol, hydrocarbon oil, wax and mixtures thereof.

9. An explosive composition according to claim 2, wherein the nitrate or equivalent ion is present essentially in the form of hydrazinium nitrate.

10. An explosive composition according to claim 2, wherein said nitrate ion or equivalent is present in a form consisting essentially of a mixture of hydrazinium nitrate and ammonium nitrate.

11. An explosive composition according to claim 2, wherein said nitrate ion or equivalent is present in the form of a mixture of stable hydronitrogen salts together with one or more metal salts in minor proportion by weight.

12. An explosive composition according to claim 11, wherein said one or more metal salts is selected from the group consisting of alkali metal nitrates, calcium nitrate, aluminum nitrate, alkali metal perchlorates, calcium perchlorate, and mixtures thereof.

13. The explosive composition of claim 5, at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium, with the aluminum particles being present in substantially stoichiometric proportion with respect to the oxidizer.

Aluminum particles From about 20% to about 35%. NH and NH,+ to about N H and N H From about to about 30%. NO or equivalent From about 25% to about 55%.

wherein the nitrate anion'or equivalent is present in one or more compounds selected from the group consisting of nitrate(s) and mixtures thereof with minor amounts of perchlorate(s).

-17. An explosive composition according to claim 16, wherein the aluminum particles are present in substantially stoichiometric proportion with respect to the nitrate or equivalent. r

18. The explosive composition of claim 16, at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium.

19. The explosive composition of claim 16, further comprising a thickening and/or gelling agent present in an amount sufiici ent to provide the composition with the rheological properties of a solid and insufficient to render a composition nondetonatable.

20. A'n explosive" composition according to claim 19, wherein said gelling agent is present in an amount less than about 5%, and is selected from the group consisting of expanded silica, Guartec, and mixtures thereof.

21. An explosive composition according to claim 16, further comprising adesensitizi'ng' agent, present in an amount insufficient to render thecomposition nondetonatable.

22. An explosive composition according to claim 21, wherein said desensitizing agent is present in an amount less than about 10% by weight and is selected from the group consisting of water, glycerin, glycol, hydrocarbon oil, wax and mixtures thereof.

23. An explosive composition according to claim 16, wherein the nitrate or equivalent ion is present essentially in the form of hydraziniumnitrate- 24. An explosivecomposition according to claim 16, wherein said nitrate ion or equivalent is present in a form consisting essentially of a mixture of hydrazinium nitrate and ammonium nitrate.

r 25. An explosive composition according to claim 16, wherein said nitrate ion or equivalent is present in the form of a mixture of stable hydronitrogen salts together with one or more metal salts in minor proportion by weight. v p

' '26. An explosive composition'according to claim 25, wherein said one or more metal salts is selected from the group consisting of alkali metal nitrates, calcium nitrate, aluminum nitrate, alkali-metal perchlorates, calcium perchlorates, and mixtures thereof.

27. The explosive composition of claim 19, at least principally comprisingaluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium, with the aluminum particles. being present in substantially stoichiometric proportion with respect to the oxidizer.

28. An explosive composition according to claim 27, wherein said gelling agent is selected from the group consisting of expanded silica; Guartec, and mixtures thereof.

29. An explosive composition according to claim 28,

further comprising a desensitizing agent, present in an amount insufiicient to render the composition nondetonatable.

30. An explosive composition comprising the following constituents, present in approximately the following relative percentages by Weight:

Percent Aluminum particles 33 NH3 and NH4+ N2H4 and N2H5+ NO or equivalent 38 wherein the nitrate anion or equivalent is present in one or more compounds selected from the group consisting of nitrate(s) and mixtures thereof with minor amounts of perchlorate(s).

31. The explosive composition of claim 30, at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonia with the hydrazinium and ammonium ions in labile equilibrium.

32. The explosive composition of claim 30, further comprising a thickening and/or gelling agent present in the amount of less than about 5% by Weight.

33. An explosive composition according to claim 30, further comprising a desensitizing agent, present in an amount insufficient to render the composition nondetonatable.

34. An explosive composition according to claim 30, wherein said nitrate ion or equivalent is present in a form consisting essentially of a mixture of hydrazinium nitrate and ammonium nitrate.

35. The explosive composition of claim 32,*at least principally comprising aluminum particles substantially uniformly dispersed in hydrazinium nitrate and ammonium nitrate dissolved in hydrazine and ammonium with the hydrazinium and ammonium ions in labile equilibnum.

36. An explosive composition according to claim 35, wherein said gelling agent is a mixture of expanded silica and Guartec.

37. An explosive composition according to claim 36, further comprising a hydrocarbon oil desensitizing agent, present in an amount insuflicient to render the composition nondetonatable.

38. The method of compounding an explosive composition, comprising:

(a) preparing a first non-explosive liquid component selected from the group consisting of hydrazine and hydrazine having a non-explosive amount of one or more oxidizer salts dissolved therein;

(b) preparing a second, normally non-explosive solid component at least principally comprising one or more oxidizer salts in particulate form;

(c) mixing the above first component with the above second component with adequate agitation to cause at least a substantial portion of the second component to dissolve in the first component and provide an explosive mixture; and I (d) adding to the mixture finely divided aluminum powder while maintaining adequate agitation to provide a substantially homogeneous distribution of the aluminum powder in the explosive mixture.

39. The method of claim 38, wherein the proportions of the compounded ingredients are approximately as fol lows, expressed as relative percentages by weight:

Aluminum particles 2-45 Ammonium nitrate 2-45 Hydrazine 6-75,

40. The method of claim 38, wherein the proportions of the compounded ingredients are approximately as follows, expressed as relative percentages by weight:

1 1 41. The method of claim 38, wherein the proportions of the compounded ingredients are approximately as follows, expressed as relative percentages by weight:

Aluminum particles 33 Ammonium nitrate 48 Hydrazine 19 42. The method of claim 38, comprising mixing of the hydrazine, oxidizer salt(s) and aluminum particles under elevated temperature and/or vacuum conditions for a sufiicient time to remove at least most of the free ammonia therefrom.

43. The method of claim 42, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:

Aluminum particles 2-45 N H NO 21-95 N H 3-77 44. The method of claim 42, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:

Aluminum particles 20-35 N H NO 38-83 N H 7-30 45. The method of claim 42, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:

Aluminum particles 33 z s a 57 N H 10 Aluminum particles 2-45 Ammonium nitrate 2-45 Hydrazine 6-75 48. The method of claim 46, wherein the proportions of the compounded ingredients are approximately as follows, expressed as relative percentages by weight:

Aluminum particles -35 Ammonium nitrate 32-70 Hydrazine 15-30 49. The method of claim 46, wherein the proportions of the compounded ingredients are approximately as follows, expressed as relative percentages by weight:

Aluminum particles 33 Ammonium nitrate 48 Hydrazine 19 50. The method of claim 46, comprising mixing of the hydrazine, oxidizer salt( s) and aluminum particles under elevated temperature and/or vacuum conditions for a sufficient time to remove at least most of the free ammonia therefrom.

51. The method of claim 50, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:

Aluminum particles 2-45 N H NO 21-95 N H' 3-77 52. The method of claim 50, wherein the mixed composition'contains the following ingredients in the following relative percentages by weight:

Aluminum particles 20-3 5 N H NO 38-83 N H 7-30 53. The method of claim 50, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:

Aluminum particles 33 N H NO 57 N H 10 54. The method of claim 38, wherein the first nonexplosive liquid component comprises hydrazine having dissolved therein less than about 20% ammonium nitrate by weight, and wherein said second component consists essentially of ammonium nitrate.

55. The method of claim 54, wherein the proportions of the compounded ingredients are approximately as follows, expressed as relative percentages by weight:

Aluminum particles 2-45 Ammonium nitrate 2-45 Hydrazine 6-75 56. The method of claim 54, wherein the proportions of the compounded ingredients are approximately as follows, expressed as relative percentages by weight:

Aluminum particles 20-35 Ammonium nitrate 32-70 Hydrazine 15-30 57. The method of claim 54, wherein the proportions of the compounded ingredients are approximately as follows, expressed as relative percentages by weight:

Aluminum particles 33 Ammonium nitrate 48 Hydrazine 19 58. The method of claim 54, comprising mixing of the hydrazine, ammonium nitrate and aluminum particles under elevated temperature and/or vacuum conditions for a sufficient time to remove at least most of the free ammonia therefrom.

59. The method of claim 58, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:

Aluminum particles 2-45 60. The method of claim 58, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:

Aluminum particles 20-35 N H NO 38-83 N H 7-30 61. The method of claim 58, wherein the mixed composition contains the following ingredients in the following relative percentages by weight:

Aluminum particles 33 N H NO -57 N H 10 References Cited UNITED STATES PATENTS 2,704,706 3/ 1955 Audrieth 149-36 XR 2,978,864 4/1961 Stengel 14936 XR 3,061,489 10/1962 Stengel et al. 14936 3,197,348 7/ 1965 Skolnik 14936 XR BENJAMIN R. PADGETT, Primary Examiner US. Cl. X.R. 149-41, 42, 43, 44, 74 

